MARC details
| 000 -LEADER |
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| fixed length control field |
43230cam a2200241 a 4500 |
| 001 - CONTROL NUMBER |
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| control field |
14681151 |
| 005 - DATE AND TIME OF LATEST TRANSACTION |
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| control field |
20200908111254.0 |
| 008 - FIXED-LENGTH DATA ELEMENTS--GENERAL INFORMATION |
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| fixed length control field |
061227s2007 flua b 001 0 eng |
| 020 ## - INTERNATIONAL STANDARD BOOK NUMBER |
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| International Standard Book Number |
9781574447798 (alk. paper) |
| 020 ## - INTERNATIONAL STANDARD BOOK NUMBER |
|---|
| International Standard Book Number |
1574447793 (alk. paper) |
| 040 ## - CATALOGING SOURCE |
|---|
| Transcribing agency |
DLC |
| 082 00 - DEWEY DECIMAL CLASSIFICATION NUMBER |
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| Classification number |
547.7 |
| Edition number |
22 |
| Item number |
H6335 |
| 100 1# - MAIN ENTRY--PERSONAL NAME |
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| Personal name |
Hiemenz, Paul C., |
| 245 10 - TITLE STATEMENT |
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| Title |
Polymer chemistry |
| Statement of responsibility, etc |
/ Paul C. Hiemenz, Timothy P. Lodge. |
| 250 ## - EDITION STATEMENT |
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| Edition statement |
2nd ed. |
| 260 ## - PUBLICATION, DISTRIBUTION, ETC. (IMPRINT) |
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| Place of publication, distribution, etc |
Boca Raton : |
| Name of publisher, distributor, etc |
CRC Press, |
| Date of publication, distribution, etc |
2007 |
| 300 ## - PHYSICAL DESCRIPTION |
|---|
| Extent |
xvii, 587 p. : |
| Other physical details |
ill. ; |
| Dimensions |
27 cm. |
| 650 #0 - SUBJECT ADDED ENTRY--TOPICAL TERM |
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| Topical term or geographic name as entry element |
Polymers. |
| 650 #0 - SUBJECT ADDED ENTRY--TOPICAL TERM |
|---|
| Topical term or geographic name as entry element |
Polymerization. |
| 700 1# - ADDED ENTRY--PERSONAL NAME |
|---|
| Personal name |
Lodge, Timothy. |
| 942 ## - ADDED ENTRY ELEMENTS (KOHA) |
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| Koha item type |
Books |
| 505 0# - FORMATTED CONTENTS NOTE |
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| Formatted contents note |
1 Introduction to Chain Molecules .................................................................1<br/>1.1 Introduction................................................................................................................... 1<br/>1.2 How Big is Big? ............................................................................................................ 3<br/>1.2.1 Molecular Weight ..............................................................................................3<br/>1.2.2 Spatial Extent.....................................................................................................4<br/>1.3 Linear and Branched Polymers, Homopolymers, and Copolymers ............................. 7<br/>1.3.1 Branched Structures ...........................................................................................7<br/>1.3.2 Copolymers ........................................................................................................9<br/>1.4 Addition, Condensation, and Natural Polymers.......................................................... 11<br/>1.4.1 Addition and Condensation Polymers .............................................................11<br/>1.4.2 Natural Polymers .............................................................................................13<br/>1.5 Polymer Nomenclature ................................................................................................ 18<br/>1.6 Structural Isomerism.................................................................................................... 20<br/>1.6.1 Positional Isomerization ..................................................................................20<br/>1.6.2 Stereo Isomerization ........................................................................................21<br/>1.6.3 Geometrical Isomerization...............................................................................22<br/>1.7 Molecular Weights and Molecular Weight Averages................................................. 24<br/>1.7.1 Number-, Weight-, and z-Average Molecular Weights ..................................25<br/>1.7.2 Polydispersity Index and Standard Deviation .................................................26<br/>1.7.3 Examples of Distributions ...............................................................................28<br/>1.8 Measurement of Molecular Weight............................................................................. 31<br/>1.8.1 General Considerations....................................................................................31<br/>1.8.2 End Group Analysis.........................................................................................32<br/>1.8.3 MALDI Mass Spectrometry ............................................................................35<br/>1.9 Preview of Things to Come......................................................................................... 37<br/>1.10 Chapter Summary ........................................................................................................ 38<br/>References............................................................................................................................... 41<br/>Further Readings...................................................................................................................... 41<br/>2 Step-Growth Polymerization......................................................................43<br/>2.1 Introduction................................................................................................................... 43<br/>2.2 Condensation Polymers: One Step at a Time ............................................................... 43<br/>2.2.1 Classes of Step-Growth Polymers .....................................................................43<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page x 20.10.2006 1:22pm<br/>2.2.2 First Look at the Distribution of Products ........................................................44<br/>2.2.3 A First Look at Reactivity and Reaction Rates ................................................46<br/>2.3 Kinetics of Step-Growth Polymerization ...................................................................... 49<br/>2.3.1 Catalyzed Step-Growth Reactions.....................................................................50<br/>2.3.2 How Should Experimental Data Be Compared with<br/>Theoretical Rate Laws? .....................................................................................52<br/>2.3.3 Uncatalyzed Step-Growth Reactions.................................................................53<br/>2.4 Distribution of Molecular Sizes .................................................................................... 56<br/>2.4.1 Mole Fractions of Species .................................................................................56<br/>2.4.2 Weight Fractions of Species..............................................................................58<br/>2.5 Polyesters ....................................................................................................................... 60<br/>2.6 Polyamides ..................................................................................................................... 64<br/>2.7 Stoichiometric Imbalance .............................................................................................. 67<br/>2.8 Chapter Summary .......................................................................................................... 71<br/>Problems ................................................................................................................................. 71<br/>References............................................................................................................................... 76<br/>Further Reading ....................................................................................................................... 76<br/>3 Chain-Growth Polymerization....................................................................77<br/>3.1 Introduction .................................................................................................................... 77<br/>3.2 Chain-Growth and Step-Growth Polymerizations: Some Comparisons....................... 77<br/>3.3 Initiation ......................................................................................................................... 79<br/>3.3.1 Initiation Reactions ............................................................................................80<br/>3.3.2 Fate of Free Radicals .........................................................................................81<br/>3.3.3 Kinetics of Initiation ..........................................................................................82<br/>3.3.4 Photochemical Initiation ....................................................................................84<br/>3.3.5 Temperature Dependence of Initiation Rates....................................................85<br/>3.4 Termination.................................................................................................................... 86<br/>3.4.1 Combination and Disproportionation ................................................................86<br/>3.4.2 Effect of Termination on Conversion to Polymer ............................................88<br/>3.4.3 Stationary-State Radical Concentration ............................................................89<br/>3.5 Propagation .................................................................................................................... 90<br/>3.5.1 Rate Laws for Propagation ................................................................................91<br/>3.5.2 Temperature Dependence of Propagation Rates ...............................................92<br/>3.5.3 Kinetic Chain Length.........................................................................................94<br/>3.6 Radical Lifetime ............................................................................................................ 96<br/>3.7 Distribution of Molecular Weights................................................................................ 99<br/>3.7.1 Distribution of i-mers: Termination by Disproportionation .............................99<br/>3.7.2 Distribution of i-mers: Termination by Combination.....................................102<br/>3.8 Chain Transfer ............................................................................................................. 104<br/>3.8.1 Chain Transfer Reactions ................................................................................105<br/>3.8.2 Evaluation of Chain Transfer Constants .........................................................106<br/>3.8.3 Chain Transfer to Polymer ..............................................................................108<br/>3.8.4 Suppressing Polymerization ............................................................................109<br/>3.9 Chapter Summary ........................................................................................................ 110<br/>Problems ............................................................................................................................... 110<br/>References............................................................................................................................. 114<br/>Further Reading ..................................................................................................................... 115<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xi 20.10.2006 1:22pm<br/>4 Controlled Polymerization .......................................................................117<br/>4.1 Introduction................................................................................................................ 117<br/>4.2 Poisson Distribution for an Ideal Living Polymerization ......................................... 118<br/>4.2.1 Kinetic Scheme..............................................................................................119<br/>4.2.2 Breadth of the Poisson Distribution ..............................................................122<br/>4.3 Anionic Polymerization ............................................................................................. 126<br/>4.4 Block Copolymers, End-Functional Polymers, and Branched<br/>Polymers by Anionic Polymerization........................................................................ 129<br/>4.4.1 Block Copolymers .........................................................................................129<br/>4.4.2 End-Functional Polymers ..............................................................................133<br/>4.4.3 Regular Branched Architectures....................................................................135<br/>4.5 Cationic Polymerization ............................................................................................ 137<br/>4.5.1 Aspects of Cationic Polymerization ..............................................................138<br/>4.5.2 Living Cationic Polymerization ....................................................................140<br/>4.6 Controlled Radical Polymerization ........................................................................... 142<br/>4.6.1 General Principles of Controlled Radical Polymerization............................142<br/>4.6.2 Particular Realizations of Controlled Radical Polymerization .....................144<br/>4.6.2.1 Atom Transfer Radical Polymerization.........................................144<br/>4.6.2.2 Stable Free-Radical Polymerization (SFRP).................................145<br/>4.6.2.3 Reversible Addition-Fragmentation Transfer (RAFT)<br/>Polymerization ...............................................................................145<br/>4.7 Polymerization Equilibrium....................................................................................... 147<br/>4.8 Ring-Opening Polymerization ................................................................................... 150<br/>4.8.1 General Aspects .............................................................................................150<br/>4.8.2 Specific Examples of Living Ring-Opening Polymerizations......................152<br/>4.8.2.1 Poly(Ethylene Oxide) ....................................................................152<br/>4.8.2.2 Polylactide......................................................................................153<br/>4.8.2.3 Poly(dimethyl siloxane).................................................................154<br/>4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP) .....................155<br/>4.9 Dendrimers................................................................................................................. 156<br/>4.10 Chapter Summary ...................................................................................................... 160<br/>Problems ............................................................................................................................... 161<br/>References............................................................................................................................. 163<br/>Further Reading ..................................................................................................................... 163<br/>5 Copolymers, Microstructure, and Stereoregularity................................165<br/>5.1 Introduction................................................................................................................ 165<br/>5.2 Copolymer Composition............................................................................................ 166<br/>5.2.1 Rate Laws ......................................................................................................166<br/>5.2.2 Composition versus Feedstock ......................................................................168<br/>5.3 Reactivity Ratios........................................................................................................ 170<br/>5.3.1 Effects of r Values.........................................................................................171<br/>5.3.2 Relation of Reactivity Ratios to Chemical Structure....................................173<br/>5.4 Resonance and Reactivity.......................................................................................... 175<br/>5.5 A Closer Look at Microstructure .............................................................................. 179<br/>5.5.1 Sequence Distributions ..................................................................................180<br/>5.5.2 Terminal and Penultimate Models ................................................................183<br/>5.6 Copolymer Composition and Microstructure: Experimental Aspects ...................... 185<br/>5.6.1 Evaluating Reactivity Ratios from Composition Data .................................186<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xii 20.10.2006 1:22pm<br/>5.6.2 Spectroscopic Techniques..............................................................................188<br/>5.6.3 Sequence Distribution: Experimental Determination ...................................190<br/>5.7 Characterizing Stereoregularity ................................................................................. 193<br/>5.8 A Statistical Description of Stereoregularity ............................................................ 196<br/>5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance................................... 200<br/>5.10 Ziegler¿Natta Catalysts ............................................................................................. 205<br/>5.11 Single-Site Catalysts .................................................................................................. 208<br/>5.12 Chapter Summary ...................................................................................................... 211<br/>Problems ............................................................................................................................... 212<br/>References............................................................................................................................. 216<br/>Bibliography .......................................................................................................................... 216<br/>6 Polymer Conformations ...........................................................................217<br/>6.1 Conformations, Bond Rotation, and Polymer Size..................................................... 217<br/>6.2 Average End-to-End Distance for Model Chains ....................................................... 219<br/>Case 6.2.1 The Freely Jointed Chain .......................................................................220<br/>Case 6.2.2 The Freely Rotating Chain .....................................................................221<br/>Case 6.2.3 Hindered Rotation Chain ........................................................................222<br/>6.3 Characteristic Ratio and Statistical Segment Length.................................................. 223<br/>6.4 Semiflexible Chains and the Persistence Length........................................................ 225<br/>6.4.1 Persistence Length of Flexible Chains............................................................227<br/>6.4.2 Worm-Like Chains ..........................................................................................228<br/>6.5 Radius of Gyration....................................................................................................... 229<br/>6.6 Spheres, Rods, and Coils ............................................................................................. 234<br/>6.7 Distributions for End-to-End Distance and Segment Density .................................... 235<br/>6.7.1 Distribution of the End-to-End Vector............................................................236<br/>6.7.2 Distribution of the End-to-End Distance.........................................................239<br/>6.7.3 Distribution about the Center of Mass ............................................................240<br/>6.8 Self-Avoiding Chains: A First Look ........................................................................... 241<br/>6.9 Chapter Summary ........................................................................................................ 242<br/>Problems ............................................................................................................................... 242<br/>References............................................................................................................................. 244<br/>Further Reading ..................................................................................................................... 245<br/>7 Thermodynamics of Polymer Solutions .................................................247<br/>7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts ..................... 247<br/>7.2 Regular Solution Theory ............................................................................................. 249<br/>7.2.1 Regular Solution Theory: Entropy of Mixing.................................................249<br/>7.2.2 Regular Solution Theory: Enthalpy of Mixing ...............................................251<br/>7.3 Flory¿Huggins Theory................................................................................................. 254<br/>7.3.1 Flory¿Huggins Theory: Entropy of Mixing by a Quick Route ......................255<br/>7.3.2 Flory¿Huggins Theory: Entropy of Mixing by a Longer Route ....................255<br/>7.3.3 Flory¿Huggins Theory: Enthalpy of Mixing ..................................................257<br/>7.3.4 Flory¿Huggins Theory: Summary of Assumptions ........................................258<br/>7.4 Osmotic Pressure ......................................................................................................... 258<br/>7.4.1 Osmotic Pressure: General Case .....................................................................259<br/>7.4.1.1 Number-Average Molecular Weight ...............................................261<br/>7.4.2 Osmotic Pressure: Flory¿Huggins Theory ......................................................263<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xiii 20.10.2006 1:22pm<br/>7.5 Phase Behavior of Polymer Solutions......................................................................... 264<br/>7.5.1 Overview of the Phase Diagram......................................................................265<br/>7.5.2 Finding the Binodal .........................................................................................268<br/>7.5.3 Finding the Spinodal........................................................................................269<br/>7.5.4 Finding the Critical Point ................................................................................270<br/>7.5.5 Phase Diagram from Flory¿Huggins Theory ..................................................271<br/>7.6 What is in x?................................................................................................................ 275<br/>7.6.1 x from Regular Solution Theory .....................................................................275<br/>7.6.2 x from Experiment...........................................................................................276<br/>7.6.3 Further Approaches to x..................................................................................278<br/>7.7 Excluded Volume and Chains in a Good Solvent ...................................................... 280<br/>7.8 Chapter Summary ........................................................................................................ 283<br/>Problems ............................................................................................................................... 284<br/>References............................................................................................................................. 287<br/>Bibliography .......................................................................................................................... 288<br/>8 Light Scattering by Polymer Solutions...................................................289<br/>8.1 Introduction: Light Waves........................................................................................... 289<br/>8.2 Basic Concepts of Scattering....................................................................................... 291<br/>8.2.1 Scattering from Randomly Placed Objects .....................................................292<br/>8.2.2 Scattering from a Perfect Crystal ....................................................................292<br/>8.2.3 Origins of Incoherent and Coherent Scattering ..............................................293<br/>8.2.4 Bragg¿s Law and the Scattering Vector ..........................................................294<br/>8.3 Scattering by an Isolated Small Molecule .................................................................. 296<br/>8.4 Scattering from a Dilute Polymer Solution................................................................. 298<br/>8.5 The Form Factor and the Zimm Equation .................................................................. 304<br/>8.5.1 Mathematical Expression for the Form Factor ...............................................305<br/>8.5.2 Form Factor for Isotropic Solutions ................................................................306<br/>8.5.3 Form Factor as qRg P 1 ..................................................................................307<br/>8.5.4 Zimm Equation ................................................................................................307<br/>8.5.5 Zimm Plot ........................................................................................................308<br/>8.6 Scattering Regimes and Particular Form Factors........................................................ 312<br/>8.7 Experimental Aspects of Light Scattering .................................................................. 314<br/>8.7.1 Instrumentation ................................................................................................316<br/>8.7.2 Calibration........................................................................................................317<br/>8.7.3 Samples and Solutions.....................................................................................319<br/>8.7.4 Refractive Index Increment .............................................................................319<br/>8.8 Chapter Summary ........................................................................................................ 320<br/>Problems ............................................................................................................................... 321<br/>Bibliography .......................................................................................................................... 325<br/>Further Reading ..................................................................................................................... 325<br/>9 Dynamics of Dilute Polymer Solutions ...................................................327<br/>9.1 Introduction: Friction and Viscosity............................................................................ 327<br/>9.2 Stokes¿ Law and Einstein¿s Law................................................................................. 330<br/>9.2.1 Viscous Forces on Rigid Spheres....................................................................331<br/>9.2.2 Suspension of Spheres .....................................................................................332<br/>9.3 Intrinsic Viscosity ........................................................................................................ 334<br/>9.3.1 General Considerations....................................................................................334<br/>9.3.2 Mark¿Houwink Equation ................................................................................336<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xiv 20.10.2006 1:22pm<br/>9.4 Measurement of Viscosity ........................................................................................ 341<br/>9.4.1 Poiseuille Equation and Capillary Viscometers ...........................................341<br/>9.4.2 Concentric Cylinder Viscometers .................................................................345<br/>9.5 Diffusion Coefficient and Friction Factor ................................................................ 346<br/>9.5.1 Tracer Diffusion and Hydrodynamic Radius................................................347<br/>9.5.2 Mutual Diffusion and Fick¿s Laws...............................................................348<br/>9.6 Dynamic Light Scattering ......................................................................................... 354<br/>9.7 Hydrodynamic Interactions and Draining ................................................................ 357<br/>9.8 Size Exclusion Chromatography............................................................................... 360<br/>9.8.1 Basic Separation Process ..............................................................................361<br/>9.8.2 Separation Mechanism ..................................................................................365<br/>9.8.3 Two Calibration Strategies ...........................................................................367<br/>9.8.3.1 Limitations of Calibration by Standards.......................................367<br/>9.8.3.2 Universal Calibration ....................................................................368<br/>9.8.4 Size Exclusion Chromatography Detectors ..................................................369<br/>9.8.4.1 RI Detector ....................................................................................369<br/>9.8.4.2 uv¿vis Detector .............................................................................370<br/>9.8.4.3 Light Scattering Detector..............................................................371<br/>9.8.4.4 Viscometer.....................................................................................372<br/>9.9 Chapter Summary...................................................................................................... 372<br/>Problems............................................................................................................................. 373<br/>References ........................................................................................................................... 378<br/>Further Reading................................................................................................................... 379<br/>10 Networks, Gels, and Rubber Elasticity .................................................381<br/>10.1 Formation of Networks by Random Cross-Linking............................................... 381<br/>10.1.1 Definitions .................................................................................................381<br/>10.1.2 Gel Point....................................................................................................383<br/>10.2 Polymerization with Multifunctional Monomers ................................................... 386<br/>10.2.1 Calculation of the Branching Coefficient.................................................387<br/>10.2.2 Gel Point....................................................................................................388<br/>10.2.3 Molecular-Weight Averages .....................................................................389<br/>10.3 Elastic Deformation ................................................................................................ 392<br/>10.4 Thermodynamics of Elasticity ................................................................................ 394<br/>10.4.1 Equation of State.......................................................................................394<br/>10.4.2 Ideal Elastomers ........................................................................................396<br/>10.4.3 Some Experiments on Real Rubbers ........................................................397<br/>10.5 Statistical Mechanical Theory of Rubber Elasticity: Ideal Case ........................... 398<br/>10.5.1 Force to Extend a Gaussian Chain ...........................................................400<br/>10.5.2 Network of Gaussian Strands....................................................................402<br/>10.5.3 Modulus of the Gaussian Network ...........................................................403<br/>10.6 Further Developments in Rubber Elasticity ........................................................... 406<br/>10.6.1 Non-Gaussian Force Law..........................................................................406<br/>10.6.2 Front Factor ...............................................................................................407<br/>10.6.3 Network Defects........................................................................................408<br/>10.6.4 Mooney¿Rivlin Equation ..........................................................................409<br/>10.7 Swelling of Gels...................................................................................................... 410<br/>10.7.1 Modulus of a Swollen Rubber ..................................................................411<br/>10.7.2 Swelling Equilibrium ................................................................................412<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xv 20.10.2006 1:22pm<br/>10.8 Chapter Summary.................................................................................................... 414<br/>Problems............................................................................................................................. 416<br/>References ........................................................................................................................... 418<br/>Further Reading................................................................................................................... 418<br/>11 Linear Viscoelasticity .............................................................................419<br/>11.1 Basic Concepts ........................................................................................................ 419<br/>11.1.1 Stress and Strain........................................................................................421<br/>11.1.2 Viscosity, Modulus, and Compliance .......................................................421<br/>11.1.3 Viscous and Elastic Responses .................................................................422<br/>11.2 Response of the Maxwell and Voigt Elements ...................................................... 423<br/>11.2.1 Transient Response: Stress Relaxation .....................................................423<br/>11.2.2 Transient Response: Creep........................................................................426<br/>11.2.3 Dynamic Response: Loss and Storage Moduli.........................................427<br/>11.2.4 Dynamic Response: Complex Modulus and Complex Viscosity ............430<br/>11.3 Boltzmann Superposition Principle ........................................................................ 431<br/>11.4 Bead¿Spring Model................................................................................................. 433<br/>11.4.1 Ingredients of the Bead¿Spring Model.....................................................433<br/>11.4.2 Predictions of the Bead¿Spring Model.....................................................434<br/>11.5 Zimm Model for Dilute Solutions, Rouse Model for<br/>Unentangled Melts .................................................................................................. 440<br/>11.6 Phenomenology of Entanglement ........................................................................... 445<br/>11.6.1 Rubbery Plateau ........................................................................................445<br/>11.6.2 Dependence of Me on Molecular Structure ..............................................448<br/>11.7 Reptation Model...................................................................................................... 451<br/>11.7.1 Reptation Model: Longest Relaxation Time and Diffusivity...................452<br/>11.7.2 Reptation Model: Viscoelastic Properties ................................................455<br/>11.7.3 Reptation Model: Additional Relaxation Processes .................................457<br/>11.8 Aspects of Experimental Rheometry ...................................................................... 459<br/>11.8.1 Shear Sandwich and Cone and Plate Rheometers....................................459<br/>11.8.2 Further Comments about Rheometry........................................................461<br/>11.9 Chapter Summary .................................................................................................... 462<br/>Problems............................................................................................................................. 462<br/>References ........................................................................................................................... 465<br/>Further Reading................................................................................................................... 465<br/>12 Glass Transition......................................................................................467<br/>12.1 Introduction ............................................................................................................. 467<br/>12.1.1 Definition of a Glass .................................................................................467<br/>12.1.2 Glass and Melting Transitions ..................................................................468<br/>12.2 Thermodynamic Aspects of the Glass Transition .................................................. 470<br/>12.2.1 First-Order and Second-Order Phase Transitions.....................................471<br/>12.2.2 Kauzmann Temperature ............................................................................473<br/>12.2.3 Theory of Gibbs and DiMarzio ................................................................474<br/>12.3 Locating the Glass Transition Temperature ........................................................... 476<br/>12.3.1 Dilatometry................................................................................................476<br/>12.3.2 Calorimetry................................................................................................478<br/>12.3.3 Dynamic Mechanical Analysis .................................................................480<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xvi 20.10.2006 1:22pm<br/>12.4 Free Volume Description of the Glass Transition.................................................. 481<br/>12.4.1 Temperature Dependence of the Free Volume ........................................482<br/>12.4.2 Free Volume Changes Inferred from the Viscosity .................................483<br/>12.4.3 Williams¿Landel¿Ferry Equation.............................................................485<br/>12.5 Time¿Temperature Superposition........................................................................... 488<br/>12.6 Factors That Affect the Glass Transition Temperature.......................................... 493<br/>12.6.1 Dependence on Chemical Structure..........................................................493<br/>12.6.2 Dependence on Molecular Weight ...........................................................494<br/>12.6.3 Dependence on Composition ....................................................................494<br/>12.7 Mechanical Properties of Glassy Polymers ............................................................ 498<br/>12.7.1 Basic Concepts ..........................................................................................498<br/>12.7.2 Crazing, Yielding, and the Brittle-to-Ductile Transition .........................500<br/>12.7.3 Role of Chain Stiffness and Entanglements .............................................503<br/>12.8 Chapter Summary.................................................................................................... 506<br/>Problems............................................................................................................................. 507<br/>Bibliography....................................................................................................................... 510<br/>Further Reading................................................................................................................... 510<br/>13 Crystalline Polymers...............................................................................513<br/>13.1 Introduction and Overview ..................................................................................... 513<br/>13.2 Structure and Characterization of Unit Cells ......................................................... 515<br/>13.2.1 Classes of Crystals ....................................................................................515<br/>13.2.2 X-Ray Diffraction .....................................................................................517<br/>13.2.3 Examples of Unit Cells .............................................................................520<br/>13.3 Thermodynamics of Crystallization: Relation of Melting Temperature<br/>to Molecular Structure ............................................................................................ 523<br/>13.4 Structure and Melting of Lamellae......................................................................... 528<br/>13.4.1 Surface Contributions to Phase Transitions..............................................528<br/>13.4.2 Dependence of Tm on Lamellar Thickness...............................................529<br/>13.4.3 Dependence of Tm on Molecular Weight .................................................532<br/>13.4.4 Experimental Characterization of Lamellar Structure .............................534<br/>13.5 Kinetics of Nucleation and Growth ........................................................................ 538<br/>13.5.1 Primary Nucleation ...................................................................................539<br/>13.5.2 Crystal Growth ..........................................................................................541<br/>13.6 Morphology of Semicrystalline Polymers .............................................................. 547<br/>13.6.1 Spherulites .................................................................................................547<br/>13.6.2 Nonspherulitic Morphologies....................................................................550<br/>13.7 Kinetics of Bulk Crystallization ............................................................................. 554<br/>13.7.1 Avrami Equation .......................................................................................554<br/>13.7.2 Kinetics of Crystallization: Experimental Aspects ..................................559<br/>13.8 Chapter Summary.................................................................................................... 564<br/>Problems............................................................................................................................. 565<br/>References ........................................................................................................................... 568<br/>Further Reading................................................................................................................... 568<br/>Appendix .........................................................................................................569<br/>A.1 Series Expansions ...............................................................................................................569<br/>A.2 Summation Formulae..........................................................................................................570<br/>Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xvii 20.10.2006 1:22pm<br/>A.3 Transformation to Spherical Coordinates...........................................................................571<br/>A.4 Some Integrals of Gaussian Functions ...............................................................................572<br/>A.5 Complex Numbers ..............................................................................................................574<br/> |
